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PubMed1987

DNA damage by chemically generated singlet oxygen.

A naphthalenic endoperoxide was used as a non-photochemical source of singlet oxygen (1O2) to examine some interactions between this reactive oxygen species and DNA. High molecular weight DNA (ca. 10(8) daltons) was exposed to 120 mol m-3 1O2 (cumulative concentration) and analyzed for interstrand crosslinkage by hydroxyl apatite chromatography following formamide denaturation. No evidence for 1O2-induced interstrand crosslinking was obtained. The capacity of 1O2 to generate strand breaks in single-stranded (ss) and double-stranded (ds) DNA was investigated by sucrose gradient centrifugation analysis of bacteriophage phi X174 DNA. No direct strand breaks could be detected at neutral pH, whereas extensive strand breakage was observed after treatment with alkali. Possible biological consequences of 1O2-exposure were assessed by examining the plaque-forming capacity of ss and ds phi X174 DNA molecules using wildtype Escherichia coli spheroplasts as recipients. Without any further treatment with heat or alkali, exposure to the endoperoxide resulted in a time- and dose-dependent inactivation, ss DNA being considerably more sensitive than ds DNA. From the present results and those reported earlier (Nieuwint et al.,) we infer that 1O2-induced inactivation of phi X174 DNA is not due to DNA backbone breakage nor to interstrand crosslinking, but rather to some form of damage to the base or sugar moiety of the DNA, the exact nature of which remains to be elucidated.

Bacteriophage phi X 174↗
PubMed1990

Redox properties of phenols, their relationships to singlet oxygen quenching and to their inhibitory effects on benzo(a)pyrene-induced neoplasia.

The inhibitory effects of synthetic phenolic compounds on benzo(a)pyrene-induced neoplasia of the mouse forestomach have been measured by Wattenberg et al. The efficiency of this inhibition has been estimated for each phenol, using R, the ratio of the number of tumors per mouse in the protected group over the number of tumours per mouse in the control group. We have observed a linear correlation between the chemoprotection efficiency R and the logarithm of the rate of quenching of singlet oxygen, k, by this family of phenols, log k being itself correlated with the one-electron oxidation potential of the phenols. These correlations suggest a charge transfer mechanism for the inhibition of neoplasia induced by benzo(a)pyrene. The correlations described provide a theoretical basis for scaling the inhibitors of mutagenicity induced by polycyclic aromatic compounds in terms of their oxidation potentials.

Animals↗
PubMed1992

Generation of singlet oxygen and hydroxyl radical from sodium chlorite and lactic acid.

Reperfusion of ischemic tissue is associated with the formation of hydroxyl radical (OH.). In this report, a novel mechanism for (OH.) generation from (1O2) is proposed based on the experimental evidence from the present study. A number of experiments were performed which conclusively demonstrated the formation of 1O2 from the reaction of lactic acid and hypohalite radical. Singlet oxygen attacks the unsaturated olefinic derivatives, which are also formed during reperfusion of ischemic tissue. The reaction between 1O2 and olefinic compounds produces hydroperoxides, which ultimately form OH. radical. The validity of the above mechanism of OH. radical formation is warranted from our experimental results.

Alkenes↗
PubMedDate not supplied

[Photosensitized luminescence of singlet oxygen in solution].

The Photoinduced afterglow of singlet oxygen was found in air saturated solutions of protoporphyrin and naphtacene in carbon tetrachloride. The excitation spectra coincide with the absorption spectra of the pigments. The lifetime is near to 7 msec, the quantum yield--to 3-10(-5). The emission maximum lies at 1270 nm. The data suggest that the luminescence is generated by oxygen in the 1 delta g state produced by the energy transfer from triplet molecules of the pigments to O2.

Carbon Tetrachloride↗
PubMed1976

[Selectivity of lysozyme oxidation by singlet oxygen].

Peptide analysis of tryptic hydrolysates of two lysozyme forms derived from oxidation of lysozyme with singlet oxygen shows that Trp-62, located at the active site, is destroyed. This is confirmed by the protective effect of the substrate (chitin), whose presense practically prevents the oxidation. A possibility of oxidating different tryptophan residues is discussed from the view-point of their availability to the reagent.

Animals↗
PubMed1999

In vivo antioxidant activity of genistein in a murine model of singlet oxygen-induced cerebral stroke.

We evaluated the in vivo antioxidant activity of genistein in a mouse model of singlet oxygen-induced cerebral stroke. Cerebral stroke was induced in male BALB/c mice through extensive microvessel damage caused by photoactivated rose bengal dye. The photoactivation of the intravenously administered rose bengal was achieved by transcranial illumination with green light. Genistein was more active than its analogs and other antioxidants that were used as control agents. At a dose of 16 mg/kg genistein administered every 6 h from 24 h prior to irradiation until 24 h after irradiation, the average size of the cerebral lesion of genistein-treated mice was significantly smaller than that in control mice treated with the carrier DMSO (8.1 +/- 1.0 mm(2) compared to 14.6 +/- 0.7 mm(2), P < 0.001). Our findings provide experimental evidence that genistein could be useful for the prevention of cerebral stroke and other pathological conditions caused by reactive oxygen species.

Animals↗
PubMed1999

Reactivity of singlet oxygen with tryptophan residues and with melittin in liposome systems.

The reactivity of singlet oxygen, 1O2, with amino acids, polypeptides and proteins has been studied extensively in solution, in micelles and also in vesicles. Here we attempt to examine its reactivity with N-acetyltryptophan amide (NATA), with a tryptophan residue with a long aliphatic chain attached, Trp(CH2)16, and with melittin--a small membrane protein--in a solution containing liposomes. In such a heterogeneous system the sensitizer and/or the tryptophan residue can be located in the ambient D2O, in the liposome membrane or at the membrane-solution interface. The sensitizer meso-tetra(N-methyl-4 pyridyl)porphine tetratosylate (mTPTT) is located in the aqueous phase while hematoporphyrin (HP) is embedded in the membrane. The quenching of 1O2 by the tryptophan residues and by melittin in solution, when using either of the sensitizers, was compared with the data in the liposome-containing system. It was found that the location of the sensitizer and of the quencher in the liposome membrane or in the surrounding solution greatly affects the quenching rate constants of 1O2.

Kinetics↗
PubMed1999

Singlet oxygen toxicity is cell line-dependent: a study of lipid peroxidation in nine leukemia cell lines.

Singlet oxygen (1O2) can be quenched by water, lipids, proteins, nucleic acids and other small molecules. Polyunsaturated fatty acids (PUFA) of cells principally quench 1O2 by chemical mechanisms, producing lipid hydroperoxides, while proteins physically and chemically quench 1O2. Because cell lines can have different PUFA and protein levels, we hypothesized that 1O2 toxicity will vary between cell lines. We used Photofrin as a source of 1O2. Exposure of nine different leukemia cell lines (CEM, HEL, HL-60, K-562, KG-1, L1210, Molt-4, THP-1 and U-937) to Photofrin and light results in changes in membrane permeability (trypan blue) that vary with cell line. The greater the lipid content of the cell line, the less susceptible they are to membrane damage. When the cell media was supplemented with docosahexaenoic acid (DHA, 22:6), the overall unsaturation of cellular lipids increased. Photofrin and light resulted in increased radical formation in these supplemented cells compared to controls; however, there was no difference in membrane permeability between DHA-supplemented and control cells. Lipid-derived radical formation (electron paramagnetic resonance spin trapping) was cell line dependent; but no correlation between lipid content of cells and radical formation was found. However, we found that the greater the protein content of cells the more they were protected against membrane damage induced by Photofrin photosensitization. This suggests that cellular proteins are a key target for 1O2-mediated toxicity. A remarkable observation is that cell size correlates inversely with ability of cells to cope with a given flux of 1O2.

Animals↗
PubMed2000

Increased endogenous ascorbyl free radical formation with singlet oxygen scavengers in reperfusion injury: an EPR and functional recovery study in rat hearts.

The objective of this study was to investigate the effect of singlet oxygen ((1)O2) scavengers on functional recovery and ascorbyl free radical (AFR) formation in isolated ischemic rat hearts. Hearts were subjected to 40 min. of global ischemia followed by 30 min. of reperfusion. Hemodynamics were measured as heart rate (HR), coronary flow (CF), left ventricular developed pressure (LVDP) and contractility (dP/dt). Electron paramagnetic resonance (EPR) spectroscopy was used to measure AFR release in coronary perfusate during the first two min. of reperfusion as a function of ROS scavengers. Relative to ischemic controls the administration of the (1)O2 scavengers 2,2,6,6-tetramethyl-4-piperidone x HCl (4-oxo-TEMP), carnosine (beta-alanyl-L-histidine) or a combination of the two significantly improved functional recovery as measured by LVDP. While no AFR signal was detected in coronary perfusate collected during preischemic perfusion with and without (1)O2 scavengers, the AFR background signal due to ischemia was significantly increased with the (1)O2 and *O2- scavengers. No such increase was observed with the hydroxyl radical (*OH) scavenger mannitol. Besides the AFR increase with the (1)O2 and *O2- scavengers the functional recovery was only significantly improved with the (1)O2 scavengers. In contrast to previous AFR studies we found with endogenous AFR that an increased AFR formation is not necessarily only reflecting increased oxidative stress but can also report improved functional recovery. Combining the hemodynamic data with increased AFR formation in the presence of several different ROS scavengers gives supportive evidence for (1)O2 also being involved in reperfusion injury.

Animals↗
PubMed2000

Failure of carboxymethylglucan to inhibit oxidative DNA damage induced by hydroxyl radicals or singlet oxygen.

The ability of carboxymethylglucan (CMG), a high molecular water-soluble derivative of glucan, was evaluated to act as a scavenger of reactive oxygen species. Hydrogen peroxide and methylene blue plus visible light, well-defined oxidant factors, were used as a model agents for induction ofoxidative DNA damage in CaCo-2 cells. Both hydrogen peroxide and visible light gave rise to dose-dependent increase of DNA damage mediated by hydroxyl radicals (*OH) or singlet oxygen (1O2), respectively. While DNA lesions generated by hydrogen peroxide dominated by strand breakage, exposure of CaCo-2 cells to visible light led mainly to base modifications sensitive to formamidopyrimidine DNA-glycosylase (Fpg). Neither CMG nor ascorbic acid, a known antioxidant, induced any DNA damage in CaCo-2 cells. Pretreatment of cells with ascorbic acid prior to H2O2 or visible light exposure resulted into statistically significant reduction of DNA lesions induced by particular agent. However, pretreatment of CaCo-2 cells with CMG in concentration range from 0.01 microM to 1 microM reduced neither the level of strand breaks induced by hydrogen peroxide nor the number of Fpg-sensitive base modifications generated by visible light.

Antioxidants↗
PubMed2000

Sensitized photooxygenation and peroxidase-catalyzed inactivation of xanthine oxidase--evidence of cysteine damage by singlet oxygen.

Xanthine oxidase (XO) has been investigated for its decreased activity in several cancerous tissues and constitutive generation of reactive oxygen species (ROS) in vivo seems to contribute significantly to its inactivation. Singlet oxygen (1O2) production has been suggested to be relevant when considering folic acid metabolism by cancer cells. Thus, the susceptibility of XO to inactivation by 1O2 generated either by the bioenergized systems folic acid/peroxidase/GSH/Mn2+/O2 and malonaldehyde/peroxidase/Mn2+/O2 or by methylene blue (MB) or eosin-sensitized photooxygenation was studied. Our results showed that other ROS were also responsible for XO inactivation when MB was used. In contrast, eosin produced almost exclusively 1O2. Kinetic studies of XO oxidation in the malonaldehyde/peroxidase system showed that histidine (His) is a competitive inhibitor with respect to XO. A similar result was observed in the eosin-photosensitized process, suggesting the involvement of 1O2 in both processes. In addition, an efficient quenching of XO oxidation by guanosine in the folic acid/peroxidase system was observed. Amino acid analysis revealed that cysteine (Cys) is more affected than other XO amino acids also prone to oxidation such as tyrosine (Tyr), methionine (Met) and His. These results indicate that 1O2 may cause oxidative damage to the Cys residues of XO, with loss of enzyme activity. Alteration of the flavin prosthetic site is hypothesized.

Amino Acids↗
PubMed2001

[Ground and first singlet excited dissociation constants of 4-methylumbelliferone: application for indirect spectrofluorimetry of nitriles and nitrosamines].

The light adsorption process provides important changes in the electronic configuration of molecules. For phenolic derivatives, light adsorption contributes to acidity in the excited state. In aqueous medium, excitation of the molecular form (ArOH) undergoes dissociation at the first singlet excited state and subsequent fluorescence emission occurs from the excited ionized form (ArO-*). The emission is higher than from the molecular form and exhibits a shift to the red. The combination of these two phenomena allowed simultaneous increase in selectivity and sensitivity. In addition this method allowed an easy quantification of 4-methylumbelliferone at the nanomolar level and consequently trace levels of nitrates and N-nitrosamines after diazotization and/or denitrozation.

Chemical Phenomena↗
PubMed2002

Detection of vitamin C-induced singlet oxygen formation in oxidized LDL using MCLA as a chemiluminescence probe.

In this study, it was observed that addition of vitamin C (vit C) to oxidized low-density lipoprotein (Ox-LDL) by cupric ions (Cu2+) could result in the formation of singlet oxygen (1O2). In experiments, 1O2 was detected by chemiluminescence method using a Cypridina luciferin analog, 2-methyl-6-(p-methoxyphenyl)-3, 7-dihydroimidazo [1, 2-a] pyrazin-3-one (MCLA), as a selective and sensitive chemiluminescence probe. Additional experimental evidence for the formation of 1O2 came from the quenching effect of sodium azide (NaN3) on vit C-induced chemiluminescence in the reaction mixture of LDL-Cu(2+)-MCLA. Analysis based on the experimental results demonstrated the plausible reaction mechanism is that vit C first converts Cu2+ to its reduced state and vit C becomes vit C radical itself, thereby stimulating the formation of peroxyl and alkoxyl radicals, and bimolecular reaction of peroxyl radicals results in 1O2 production in the systems studied.

Ascorbic Acid↗
PubMed1991

Molecular determinants of singlet oxygen binding by anthraquinones in relation to their redox cycling activity.

A series of model anthraquinones with varying symmetry of pi-electron density distribution have been examined to verify our previous hypothesis concerning the essential role of quinone-singlet oxygen complex formation by asymmetric anthraquinones in their peroxidating properties. Comparison of the results of enzymatic studies using NADH dehydrogenase with those of cyclovoltammetric measurements fully confirmed the assumption that one-electron transfer mediation is facilitated by the preceding quinone-oxygen complex formation. To extend the scope of the molecular determinants of oxygen binding found in our previous studies, CNDO/2 and molecular electrostatic field (MEF) calculations have been performed. It has been concluded that the analysis of molecular electrostatic field as well as the dipole moment components has to be taken into account to judge whether a mutual orientation of the quinone and oxygen molecule can be reached which enables binding to occur. The second important factor is the appropriate symmetry of the quinone outer filled orbitals which assures that binding is not forbidden by the Woodward-Hoffman rules. These characteristics also explain the lack of oxygen binding by some asymmetric anthraquinones. The efficient electron transfer mediation be anthraquinones requires, beside the formation of the intermediate quinone-oxygen complex, effective catalysis of this process by oxidoreductase enzyme. The results obtained with model anthraquinones indicated that compounds with more than one phenolic group and an unsubstituted quinone carbonyl are good NADH dehydrogenase substrates. Imino derivatives and compounds with a reduced number or without free phenolic groups exhibit low affinity towards the enzyme.

Anthraquinones↗
PubMed1986

Singlet oxygen mutagenicity induced in the lac operon.

We have studied the specificity of singlet oxygen (1O2) mutagenesis in single-stranded DNA phage by analysing 1O2-induced mutations in the lac insert of the M13 mp 19 hybrid phage. 107 lac mutants were analysed showing mainly single-base substitutions with a total of 93% and 7% of 40-50 base deletion mutations. Most of the substitutions are G----T and C----A transversions with respectively 27 and 54% of the mutations. The replicative form of the M13 mp 19 DNA (RFDNA) was used as substrate for the 1O2 reactions, there are then two types of progeny phages DNA's. As guanine residues are the targets of the oxidation, it appears that both types of transversions are provided by one type of lesion: the guanine oxidised by 1O2 is read like a thymine by E. coli DNA polymerase-I.

Bacteriophages↗
PubMed1989

[Photogeneration of singlet molecular oxygen by the components of hematoporphyrin IX derivative].

The photosensitized luminescence of singlet molecular oxygen has been studied in aqueous and alcoholic solutions of hematoporphyrin IX (HP) and di- and oligomeric components of "hematoporphyrin derivative" (photofrin II) which is known to be used as a drug in photodynamic tumor therapy. The quantum yields of 1O2 generation (gamma delta) by these compounds have been determined. It was found that the highest gamma delta values are characteristic of alcoholic and micellar detergent aqueous solutions. In detergent-free aqueous solutions containing mainly associated porphyrin molecules, gamma delta is much lower (5-30%), polymeric photofrin components being considerably less active than HP. Both localization of porphyrins in hydrophobic loci and high photosensitizing activity in lipid phase are supposed to play the key role in tumor photodestruction.

Dihematoporphyrin Ether↗
PubMedDate not supplied

[Photosensitized luminescence of singlet oxygen in aqueous solutions].

The photoluminescence of singlet oxygen has been observed in air saturated solutions of riboflavin in D2O and mixtures of D2O and H2O. The excitation spectrum coincides with the absorption spectrum of the pigment, the emission maximum lies at 1275 nm. In D2O the quantum yield is approximately 1,2 x 10(-7). H2O quenches the luminescence. Analysis of quenching has shown that the quantum yield in H2O is less than in D2O by the factor of 20.

Chemical Phenomena↗